Dyestuffs of the methine series



Patented Nov. 14, 1939 UNITED STATES PATENT OFFICE 2,179,895 DYESTUFFS OF THE METHINE SERIES No Drawing. Application April 18, 1936, Serial No. 75,226. In Germany April 26, 1935 6 Claims.

The present invention relates to new dyestuffs, more particularly it relates to dyestuffs of the methine series which may be represented by the probable general formula:

In the said formula R stands for halogenalkyl, R1 stands for hydrogen, alkyl, halogenalkyl, hydroxyalkyl, alkoxyalkyl, aralkyl or aryl. The grouping =C=X stands for the radical of a compound containing a reactive methyl or methylene group, in which the :0: portion is formed from the reactive methyl or methylene group, and the group stands in para-position to The new dyestuffs are obtainable by condensing according to the methods known per se a compound with a reactive methylene group with a para-aminoarylaldehyde of the general formula:

wherein R and R1. mean the same as stated above. The aldehydes used as starting components in the said process have been described, e. g., in the co-pending application for Letters Patent entitled Nitrogenous aromatic aldehydes, Serial No. 72,448 filed April 2, 1936, now issued as United States Patent No. dated December 20, 1938.

As further aldehydes suitable for the manufacture of our new dyestuffs there may be mentioned by way of example para-(phenylmethyl) aminobenzaldehyde and para-(ethoxyphenylmethyl) -aminobenza1dehyde.

As suitable compounds with reactive methylene groups there may be mentioned, for example, derivatives of cyanacetic acid, such as their esters, and amides, further derivatives of malonic acid, such as malonic nitrile, malonic ester, or the like, pyrazolones, indolines, alpha-methylindolines, alphaand gamma-alkylpyridines, alkylquinoline, oxytln'onaphthene, diketohydrindene, acetophenone, dinitrotoluene and so on.

The new dyestuffs have a number of technical advantages in comparison with the analogous polymethines hitherto known. In this process, by the presence of halogenalkyl radicals in the dyestuif molecule, a strong displacement of the shade tothe short-wave side of the spectrum is effected, so that tints are obtained that could 5 not be produced so far in this manner. Further the presence of hydroxyalkyl radicals effects in part an essential improvement of the solubility of the dyestuffs, so that particularly dark and abundant dyeings are obtainable. Likewise by 10 halogenalkyl, hydroxyalkyl and aryl radicals the i fastness to sublimation and to light are improved, particularly in dyeings on acetate silk, and often in a very essential degree. Our new dyestuffs are also suitable for sensitive silver 15 halide emulsions.

In this manner, new and very clear basic dyestuifs are obtainable, which according to the components employed, are suited for different purposes, as for instance for solvents, for the 20 dyeing of cellulose ethers and esters, for the manufacture of beautiful fast lakes on textiles and substrata, and also as leather dyestuffs.

The invention is illustrated by the following examples, without being restricted thereto: 25

Example 1.24 parts by weight of para-butylchloroethylaminobenzaldehyde are refluxed for a short time in about 100 parts by weight of alcohol with 11 parts by weight of cyanacetic acid ethylester and a few drops of piperidine. After 30 cooling, the dyestuff crystallizes in greenish yellow needles, which fuse,after filtering with suction and drying, at Ill-113 C. The dyestuif having the following formula:

is insoluble in water, easily soluble in alcohol, acetone, ethyl acetate or the like. The dyestuff 45 dyes acetate silk light greenish yellow tints of excellent fastness to light and sublimation. The tint is more greenish than that of the analogous dyestuif manufactured from para-diethylaminobenzaldehyde. The above specified fastness 50 properties are essentially better.

The dyestuff manufactured in the same manner from 1 mol of para-chlorethyl-methylaminobenzaldehyde+l mol of cyanacetic acid ethylester has a melting point of 108 C.; it dyes acetate silk lightgreenish yellow shades of similar fastness properties. The dyestufi corresponds to the following formula:

CH=C (CN)C O 0 (32115 The dyestulf from para-di-(chlorethyD-aminobenzaldehyde-l-cyanacetic acid ethyl ester separates in light greenish yellow needles of the melting point 171 C. It is easily soluble in hot alcohol, less soluble in the cold. The dyestufi corresponds to the following formula:

Example 2.26 parts by weight of para-(paraethoxyphenylmethyl) aminobenzaldehyde are refluxed for a short time in 250 parts by weight of alcohol with about 11 parts by weight of oyanacetic acid ethyl ester and a few drops of piperidine. After addition of about 100 parts by weight of water and cooling, the dyestuif crystallizes in small yellow needles of the melting point -91 C. which are easily soluble in alcohol, acetone, ethyl acetate or the like, and which dye cellulose ethers light orange yellow deep shades of good fastness to light and sublimation. The dyestufi corresponds to the following formula:

The dyestufi from the same aldehyde+malonic aciddinitrile is easily soluble in hot alcohol, less soluble in the cold, and it crystallizes therefrom in light orange needles of the melting point 107-109 C. The dyestuff corresponds to the following formula:

CH=C (CN):

Example 3.18 parts by weight of paramethyl-hydroxyethylamino-benzaldehyde are refluxed for a short time in about 50 parts by weight of alcohol with 11 parts by weight of cyanacetic acid ethyl ester and a few drops of piperidine, and then the alcohol is distilled off.

An orange yellow resin is obtained, which soon hardens to fine yellow crystals, which, after re crystallizing from alcohol, fuse at 93 C. The

dyestuff is extraordinarily easily soluble in alcohols, acetone, ethyl acetate and the like. It dyes shades of good fastness properties.

acetate silk excellently in light greenish yellow The dyestufi corresponds to the following formula:

The yellow dyestuff of the melting point 136-137 C. manufactured in the same manner from 1- mol each of para-hydroxy-ethylchlorethyl-amino-benzaldehyde and cyanacetic acid ethyl ester dyes acetate silk light greenish yellow shades of good fastness properties. The dyestuff corresponds to the following formula:

(wrong-o1 Example 5.24.6 parts by weight of para-di- (chlorethyl) amino-benzaldehyde are heated during 5 hours at C. with 13.1 parts by weight of methylketol in 65 parts by weight of glacial acetic acid. After water is added to the reaction mass, the condensation product separates first as a resin, soon solidifying, however, to a violet crystalline powder, which easily dissolves in alcohol, acetone or the like with a reddish violet coloration. The dyestuff corresponds to the following formula:

CHr-CHa-CI CH2CH2-Gl Example 6 .,24.6 parts by weight of para-di- (chlorethyl)-amino-benzaldehyde are refluxed during 30 minutes with 15.7 parts by weight of 3- oxythionaphthene and a few drops of piperidine in 250 parts by Weight of alcohol. The condensation product separates in orange leaflets of the melting point 214 C. The dyestuif corresponds to the following formula:

\CHFCHPCI Example 7.24.5 parts by weight of para-di- (chlorethyl) -amino-benzaldehyde are refluxed for some hours at C. with 17.5 parts by Weight of 1,3,3-trimethyl-2-methylene-indoline in parts by weight of glacial acetic acid. After pouring the reaction mass into Water and salting out with sodium chloride, the dyestufi' is obtained as a dark bronze resin, which soon hardens to splendid bright crystals. By recrystallizing from hot water, the pure dyestuff of the following formula I! II CHz-CHz-Cl CHPCHrCI is obtained. With complex phosphotungstic acids or the like, it gives a light bluish red colour lake of good fastness properties. The shade is essentially more reddish than that of the analogous dyestuif from, for instance, para-diethylaminobenzaldehyde+ 1,3,3 trimethyl- 2 -methylene-indoline. The dyestuff likewise dyes very clear shades on cellulose ether and ester, and on leather.

The dyestuff obtained in the same manner from 1 mol of para-methylchlorethylaminobenzaldehyde 1 mol of 1,3,3-trimethyl-2-methylene-indoline separates in beautiful easily soluble crystals with blue luster on the surface, and it gives more bluish dyeings than the dyestuif described above. The dyestuif corresponds to the following formula:

CH3 N Example 8.--22.5 parts by weight of paraethylchlorethyl amino orthoetolyladehyde are heated together with 17.5 parts by weight of 1,3,3-trimethyl+2-methyleneindoline in 70 parts by weight of glacial acetic acid to 100 C. during some hours, and the reaction mixture is worked up in accordance With the directions given in Example 7. There is obtained an easily soluble dyestuif in steel-blue crystals yielding light violetish red dyeings. The dyestuff corresponds to the following formula:

Example 9.21 parts by weight of para-methyl-beta-chloro-n-propylamino-benzaldehyde and 17.5 parts by weight of 1,3,3-trimethyl-2-methylene-indoline are condensed in the manner described in 60 parts by Weight of glacial acetic acid to a dyestuif separating in beautiful bluish iridescent crystals. It is easily soluble in water, alcohol and the like, and, with regard to its properties corresponds nearly to the dyestuffs described in the Examples 7 and 8, yielding bluish pink dyeings of excellent clearness. The dyestufi corresponds to the following formula:

Example 10.26 parts by weight of para- (paraethoxyphenylmethyl) amino-benzaldehyde are heated together with 24 parts by weight of 1- ethyl 3,3 dimethyl 2 methylene alpha naphthindolene in 75 parts by weight of glacial acetic acid to C. for some hours. The reaction mixture is poured into water and salted out with a saturated solution of sodium phosphate. In this manner there is obtained the dyestuff in green crystals, which are easily soluble in Water. The dyestufi dyes, e. g., acetate silk deep violet shades of very good fastness properties. The dyestufi corresponds to the following formula:

CH OH CH; We claim: 1. Dyestuffs of the general formula N-aryl-OH=C=X wherein R stands for halogenalkyl, R1 stands for a member selected from the group consisting of hydrogen, alkyl, halogenalkyl, hydroxyalkyl, alkoxyalkyl, aryl and aralkyl, the grouping =C=X stands for the radical of a compound containing a reactive group selected from the class consisting of reactive methyl and reactive methylene groups, in which the =C= portion is formed from the said reactive group, and the group stands in para-position to CH, yielding in general clear shades on cellulose acetate silk.

2. Dyestufis of the general formula N-aryl-OH=O=X wherein R stands for a halogenalkyl, R1 stands for a member selected from the group consisting of hydrogen, alkyl, halogenalkyl, hydroxyalkyl, alkoxyalkyl, aryl and aralkyl, the grouping =C=X stands for the radical of a compound containing a reactive group selected from the class consisting of reactive methyl and reactive methylene groups, in which the =C= portion is formed from the said reactive group, said compound being selected from the group consisting of cyanacetic acid esters, cyanacetic acid amides, malonitrile and alpha-methylindolines, and the group 3. Dyestufis of the general formula NarylCH=0=X R1 wherein R. and R1 stand for chlorethyl, the grouping =C=X stands for the radical of a compound containing a reactive group selected from the class consisting of reactive methyl and reactive methylene groups, in which the =C= portion is formed from the said reactive group, said compound being selected from the group consisting of cyanacetic acid esters, cyanacetic acid amides, malonitrile and alpha-methylindolines, and the group :R stands in para-position to CH, yielding in general clear shades on cellulose acetate silk.

4. The dyestufi" of the formula:

CH=C (ON)C O O CzHs dyeing acetate silk light greenish yellow tints of excellent fastness to light on sublimation.

5. The dyestuff of the formula 1 TCHa CHz-CH.O1 dyeing acetate artificial silk light bluish-red shades.

6. The dyestuff of the formula CH OH3(E CH=CHO N-CzHB HLCHLOI dyeing acetate artificial silk light violetish red shades.

WERNER MiiLLER. CARL BERRES.

Certificate of Correction Patent No. 2,179,895.

November 14, 1939. WERNER MULLER ET AL.

that error appears in the printed s numbered patent requi rlng correctlon as follows: Pa

go 3, second column, lines 15 g [SEAL] HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

